Method and system for growth of graphene nanostripes by plasma enhanced chemical vapor deposition

ABSTRACT

A method of forming vertical graphene nanostripes comprising one or several monolayers and characterized by a thickness normal to the one or several monolayers, a length orthogonal to the thickness, and a width orthogonal to the thickness includes providing a substrate, subjecting the substrate to a reduced pressure environment in a processing chamber, and providing methane gas and C 6 -containing precursor. The method also includes flowing the methane gas and the C 6 -containing precursor into the processing chamber, establishing a partial pressure ratio of the C 6 -containing precursor to methane gas in the processing chamber, and generating a plasma. The method further includes exposing at least a portion of the substrate to the methane gas, the C 6 -containing precursor, and the plasma and growing the vertical graphene nanostripes coupled to the at least a portion of the substrate, wherein the thickness of the vertical graphene nanostripes extends parallel to the substrate.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 15/900,517, filed on Feb. 20, 2018, entitled “Method and Systemfor Growth of Graphene Nanostripes by Plasma Enhanced Chemical VaporDeposition,” which claims priority to U.S. Provisional PatentApplication No. 62/563,246, filed on Sep. 26, 2017, entitled “High-yieldSingle-step Low-temperature Catalytic Growth of Graphene Nanoribbons byPlasma Enhanced Chemical Vapor Deposition,” the disclosures of which arehereby incorporated by reference in their entirety for all purposes.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH OR DEVELOPMENT

N/A

BACKGROUND OF THE INVENTION

Graphene, a monolayer of carbon atoms forming a two-dimensionalhoneycomb lattice structure, is considered a wonder material for bothscientific research and technological applications. Its uniqueelectronic, thermal, and mechanical properties and compatibility withlithographic techniques are ideal for many nano-electronic, spintronic,and mechanical applications; it is also promising for large-areaoptoelectronic devices such as touch screen displays and electrodes forphotovoltaic cells and light emitting diodes.

Graphene has been produced by exfoliation from graphite. However,graphene produced in this manner is not suitable for many applicationsdue to its inherently small size and the non-scalability of the process.Thermal CVD based on catalytic dehydrogenation of carbon precursors(e.g. methane) on transition metals (e.g. Cu, Ni, Pt, Co) is capable ofproducing graphene of technologically relevant scales. However, the needfor multiple steps and high temperatures (˜1000° C.) is incompatiblewith device fabrication and integration.

Despite the progress made related to the formation of graphene films,there is a need in the art for improved methods and systems related tographene production.

SUMMARY OF THE INVENTION

The present invention relates generally to methods and systems formaterial synthesis. More specifically, the present invention relates tomethods and systems for growing high quality graphene nanostripes usinga high-yield, single-step, low-temperature catalytic growth process.Merely by way of example, the invention has been applied to a method ofgrowing graphene nanostripes. The methods and techniques can be appliedto a variety of graphene growth systems including CMOS compatiblesemiconductor growth processes.

According to embodiments of the present invention, methods and systemsfor the growth of graphene nanostripes (GNSPs) in a single-step processare provided. As described herein, one or more substituted aromatics(e.g., 1,2-dichlorobenzene) are utilized as precursors during a plasmaenhanced chemical vapor deposition (PECVD) process that does not requireactive heating of the growth chamber. Using low plasma power (e.g., ≤60W) with a plasma size of 1˜2 cm³, GNSPs can be grown vertically withhigh yields, for example, up to (13±4) g/m² in short time periods (e.g.,20 minutes). These GNSPs exhibit high aspect ratios (from 10:1 to˜130:1) and widths from tens to hundreds of nanometers on varioustransition-metal substrates.

The inventors have demonstrated that the morphology, electronicproperties, and yields of the GNSPs can be controlled by the growthparameters (e.g., the species of seeding molecules, compositions, andflow rates of the gases introduced into the plasma, plasma power, thegrowth time, and the like).

In summary, we have developed a new high-yield single-step method forgrowing large quantity GNSPs on various transition-metal substrates bymeans of PECVD and aromatic precursors such as 1,2-dichlorobenzene(1,2-DCB) molecules. This efficient growth method does not require anyactive heating and can reproducibly produce a high yield of ˜10 g/m²within 20 minutes at a relative low plasma power of ≤60 W for a plasmasize of 1˜2 cm³. Moreover, the GNSPs thus produced can be easilytransferred from the growth substrate to any other substrates.Therefore, this new growth method is highly promising for massproduction of GNSPs. From studies of the Raman spectra, scanningelectron microscopy (SEM) images, ultraviolet photoemission spectroscopy(UPS), transmission electron microscopy (TEM) images, energy dispersionx-ray spectroscopy (EDS) and electrical conductivity of these GNSPs asfunctions of the growth parameters, we have also confirmed thehigh-quality of these GNSPs with electrical mobility ˜10⁴ cm²/V-s andfound the correlation of the properties of GNSPs with the growthparameters. Based on our experimental findings, we propose a growth andbranching mechanism of GNSPs that suggests the important role of the1,2-DCB precursor molecules in initiating the vertical growth anddetermining the morphology of GNSPs. These findings therefore open up anew pathway to large-scale, inexpensive mass production of high-qualityGNSPs for such large-scale applications as supercapacitors andphotovoltaic cells.

In comparison with our single-step PECVD growth process of high-qualitylarge graphene sheets laterally on copper substrates without activeheating, these GNSPs of large aspect ratios are grown vertically onvarious transition-metal substrates by PECVD with the addition ofsubstituted aromatics such as 1,2-dichlorobenzene (1,2-DCB),1,2-dibromobenzene (1,2-DBB), 1,8-dibromonaphthalene (1,8-DBN) andtoluene as the seeding molecules. Among these substituted aromatics, wefind that 1,2-dichlorobenzene (1,2-DCB) is most effective for the growthof GNSPs at room temperature. Therefore, we focus hereafter on thestudies of PECVD-grown GNSPs that are seeded by 1,2-DCB. The entiregrowth process occurs in a single step within less than 20 minutes at arelatively low plasma power (≤60 W for a plasma size of 1˜2 cm³), andthe resulting GNSPs exhibit large aspect ratios and high yields. Studiesof the Raman spectroscopy, scanning electron microscopy (SEM),transmission electron microscopy (TEM), energy dispersion x-rayspectroscopy (EDS), ultraviolet photoemission spectroscopy (UPS) andelectrical conductivity all confirm the high quality of the GNSPs thusobtained. Based on these experimental findings together with data fromthe residual gas analyzer (RGA) spectra and optical emissionspectroscopy (OES) taken during the plasma process, we propose a growthmechanism and suggest that the introduction of substituted aromatics inthe hydrogen plasma plays a critical role in achieving rapid verticalgrowth of GNSPs with high aspect ratios.

According to an embodiment of the present invention, a method of forminggraphene nanostripes is provided. The method includes providing asubstrate comprising at least one of copper foil or nickel foam,subjecting the substrate to a reduced pressure environment in aprocessing chamber, and providing methane gas and 1,2-dichlorobenzene(1,2-DCB) gas. The method also includes flowing the methane gas and the1,2-DCB into the processing chamber and establishing a partial pressureratio of 1,2-DCB gas to methane gas in the processing chamber. Thepartial pressure ratio is between 0 and 3. The method further includesgenerating a plasma, thereafter, exposing the at least a portion of thesubstrate to the methane gas, the 1,2-DCB gas, and the plasma, andgrowing the graphene nanostripes coupled to the at least a portion ofthe substrate.

According to another embodiment of the present invention, a method offorming graphene nanostripes is provided. The method includes providinga transition-metal substrate, subjecting the transition-metal substrateto a reduced pressure environment, and providing methane gas and aC6-containing precursor. The method also includes exposing at least aportion of the transition-metal substrate to the methane gas and theC6-containing precursor, generating a plasma, exposing the at least aportion of the transition-metal substrate to the methane gas, theC6-containing precursor, and the plasma, and growing the graphenenanostripes coupled to the at least a portion of the transition-metalsubstrate.

According to a specific embodiment of the present invention, a method offorming graphene nanostripes is provided. The method includes providinga substrate, subjecting the substrate to a reduced pressure environment,and providing methane gas. The method also includes heating a furnace toprovide 1,8-dibromonaphthalene, exposing at least a portion of thesubstrate to the methane gas and the 1,8-dibromonaphthalene, andgenerating a plasma. The method further includes exposing the at least aportion of the substrate to the methane gas, the 1,8-dibromonaphthalene,and the plasma and growing graphene nanostripes coupled to the at leasta portion of the substrate.

Numerous benefits are achieved by way of the present invention overconventional techniques. For example, embodiments of the presentinvention provide techniques for producing graphene nanostripes that areuseful for a variety of applications including energy storage,photovoltaic energy harvesting, wide-band photon detection, andconducting composite materials. Embodiments of the present invention canbe used to grow GNSPs without active heating so as to significantlyreduce the thermal budget for material fabrication. Additionally,embodiments increase the manufacturing throughput due to the single-stepgrowth process associated with the seeded PECVD method of this inventionversus typical thermal CVD processes reported by others to date.Moreover, embodiments enable the growth of high aspect ratio graphenenanostripes with high production yields and high electrical mobility incomparison with thermal CVD processes.

These and other embodiments of the invention along with many of itsadvantages and features are described in more detail in conjunction withthe text below and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified schematic diagram illustrating a PECVD system forgrowing graphene nanostripes according to an embodiment of the presentinvention.

FIG. 2 is a simplified schematic diagram illustrating a PECVD system forgrowing graphene nanostripes according to another embodiment of thepresent invention.

FIG. 3 is a simplified flowchart illustrating a method of growinggraphene nanostripes according to an embodiment of the presentinvention.

FIGS. 4A-4C are simplified schematic diagrams illustrating a seededgrowth process for graphene nanostripes according to an embodiment ofthe present invention.

FIGS. 4D-4J are simplified schematic diagrams illustrating a mechanismfor growth and branching of graphene nanostripes according to anembodiment of the present invention.

FIG. 5 is plot illustrating partial gas pressure of 1,2-DCB measured inthe RGA as a function of time during graphene nanostripe growthaccording to an embodiment of the present invention.

FIG. 6 is an SEM image of a graphene nanostripe structure grown with asmall precursor concentration ratio according to an embodiment of thepresent invention.

FIG. 7 is an SEM image of a graphene nanostripe structure grown with alarge precursor concentration ratio according to an embodiment of thepresent invention.

FIG. 8 is a Raman spectra for a graphene nanostripe structure grown witha small precursor concentration ratio according to an embodiment of thepresent invention.

FIG. 9 is a Raman spectra for a graphene nanostripe structure grown witha large precursor concentration ratio according to an embodiment of thepresent invention.

FIG. 10 is a plot illustrating partial gas pressures as a function oftime during graphene nanostripe growth with a small precursorconcentration ratio according to an embodiment of the present invention.

FIG. 11 is a plot illustrating additional partial gas pressures as afunction of time during graphene nanostripe growth with a smallprecursor concentration ratio according to an embodiment of the presentinvention.

FIG. 12 is a plot illustrating additional partial gas pressures as afunction of time during graphene nanostripe growth with a largeprecursor concentration ratio according to an embodiment of the presentinvention.

FIGS. 13A-13C are plots of ultraviolet photoemission spectroscopy datacollected under differing graphene nanostripe growth conditionsaccording to an embodiment of the present invention.

FIG. 14 shows plots of optical emission spectroscopy intensity as afunction of wavelength for PECVD-grown graphene nanostripes underdiffering graphene nanostripe growth conditions according to anembodiment of the present invention.

FIGS. 15A-15C are TEM top view images of GNSPs with successivelyincreasing resolution from large scale to atomic scale images.

FIG. 15D is a selected area diffraction (SAD) pattern of GNSPs for theregion shown in FIG. 15C.

FIGS. 15E-15G are TEM top view images of graphene nanoflowers from largescale to atomic scale images.

FIG. 15H is a SAD pattern of the sample region shown in FIG. 15Gaccording to an embodiment of the present invention.

FIG. 16 is a plot showing Energy-dispersive X-ray spectroscopy (EDS)data for different regions of a GNSP according to an embodiment of thepresent invention.

FIG. 17A illustrates optical micrographs prior to and after growth ofGNSPs according to an embodiment of the present invention.

FIG. 17B is a plot showing transmission as a function of wavelength forGNSPs according to an embodiment of the present invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The present invention relates generally to methods and systems formaterial synthesis. More specifically, the present invention relates tomethods and systems for growing high quality graphene nanostripes usinga high-yield, single-step, low-temperature catalytic growth process. Themethods and techniques can be applied to a variety of graphene growthsystems including CMOS compatible semiconductor growth processes.

Without limiting embodiments of the present invention, we refer tostructures described herein as graphene nanostripes, to indicate theirlarge aspect ratios and to differentiate these graphene nanostripes fromgraphene nanostripes that exhibit quantum confinement and from graphenenanosheets or nanowalls that are generally wider than the graphenenanostripes discussed herein.

FIG. 1 is a simplified schematic diagram illustrating a PECVD system forgrowing graphene nanostripes according to an embodiment of the presentinvention. As illustrated in FIG. 1, the system includes a processingchamber 110. The processing chamber can also be referred to as aprocessing tube. The processing chamber is fabricated from materialssuch as quartz that provide a non-reactive environment that will sustainplasma generation. In addition to quartz, other materials, includingalumina, glass, and the like can be utilized in fabricating theprocessing chamber. An RF plasma reactor 120 (e.g., an Evenson cavitysuitable for generating a microwave plasma) and an associated powersupply 122 (e.g., available from Opthos Instruments Inc.) are providedin order to generate an RF plasma (e.g., a microwave plasma in theultra-high frequency (UHF) portion of the RF spectrum, for example at2.45 GHz) in a portion of the processing chamber 110. The portion of theprocessing chamber can include all or a fraction of the processingchamber depending on the particular implementation.

Gas sources 130, 132, and 134 are illustrated in FIG. 1 and can includefewer or a greater number of sources. In the illustrated embodiment, thegas sources are CH₄, Ar, and H₂, although the present invention is notlimited to these particular gases. Mass flow controllers (MFCs) 131,133, and 135 or other suitable flow controllers are utilized to controlthe flow rate of the gases from the gas sources to the processingchamber. Additionally, a carbon containing precursor, including1,2-dichlorobenzene (1,2-DCB) or 1,2-dibromobenzene (1,2-DBB) is storedin a quartz container 136 and attached to the processing chamber via aleak valve 137 and a quarter-turn, shut-off valve 138.

An additional leak valve 139 is illustrated in FIG. 1 and can be used tocontrol the flow of the carbon source at levels below that provided byMFCs. In some embodiments, MFC 135 is operated in an open condition andthe flow of the carbon source can be controlled using a feedback loopincorporating a feedback signal from optical spectrometer 160.Alternatively, a pre-mixture of H₂ and CH₄ (or other suitable carbonsource) could be utilized. Accordingly, some embodiments utilize theoptical emission spectra to adjust the amount of the carbon source(e.g., methane) in the stream since the optical emission spectra can besensitive to very small changes in the position of the leak valve.

In order to monitor the pressure in the processing chamber 110, one ormore pressure gauges 140 and 142 can be utilized in the vacuum linesleading to the foreline trap 144 and the vacuum pump 146. Additionalvacuum elements can be utilized as appropriate to the particularapplication. Additionally, one or more vacuum control valves 148 can beutilized to control the pressure in the processing chamber.

In order to provide for characterization of the processing environmentand the graphene formation process, an optical emission spectrometer(OES) 160 is provided, illustrated as optically coupled to theprocessing chamber using a fiber optic cable 162. In addition to an OES,which can be used to control and adjust the amount of the carbon sourcein the flow stream, the OES can be used to measure the emission peaks ofgases present in the processing chamber. In some embodiments, a ratio ofa set of emission peaks can be used to monitor the growth process andproduce consistent results. In some implementations, a residual gasanalyzer (RGA) 155 is used to monitor the carbon containing precursorand by-products partial pressure. Alternatively, an optical pyrometercan be used to measure the sample temperature. In some embodiments, anoptical inspection system (for example, a mirror that provides opticalaccess to one or more surfaces of the substrate) is utilized duringgrowth to characterize the state of copper removal. Thus, in addition toan optical spectrometer, other optical inspection techniques areincluded within the scope of the present invention.

A computer 170 including a processor 172 and computer readable medium174 is provided and coupled to the MFCs, the vacuum control valve 148,the RF plasma generator 120 and power supply 122, the OES 160, and othersuitable system components in order to provide for control of thevarious system components. In some implementations, fewer or morecomponents can be coupled to the computer. The processor 172 is used toperform calculations related to controlling at least some of the vacuumpressure, gas flow rates, plasma generation, and other systemparameters. A computer readable medium 174 (also referred to as adatabase or a memory) is coupled to the processor 172 in order to storedata used by the processor and other system elements. The processor 172interacts with the optical spectrometer 160 in some embodiments, whichprovides data on the state of the substrate cleaning process, graphenedeposition process, and the like. Using the processor 172, the memory174, and the I/O interface 176, a user is able to operate the system toform graphene as described herein.

The processor 172 can be a general purpose microprocessor configured toexecute instructions and data, such as a microprocessor manufactured bythe Intel Corporation of Santa Clara, Calif. It can also be anApplication Specific Integrated Circuit (ASIC) that embodies at leastpart of the instructions for performing the method in accordance withthe present invention in software, firmware and/or hardware. As anexample, such processors include dedicated circuitry, ASICs,combinatorial logic, other programmable processors, combinationsthereof, and the like.

The memory 174 can be local or distributed as appropriate to theparticular application. Memory 174 may include a number of memoriesincluding a main random access memory (RAM) for storage of instructionsand data during program execution and a read only memory (ROM) in whichfixed instructions are stored. Thus, memory 174 provides persistent(non-volatile) storage for program and data files, and may include ahard disk drive, flash memory, a floppy disk drive along with associatedremovable media, a Compact Disk Read Only Memory (CD-ROM) drive, anoptical drive, removable media cartridges, and other like storage media.

FIG. 2 is a simplified schematic diagram illustrating a PECVD system forgrowing graphene nanostripes according to another embodiment of thepresent invention. In the embodiment illustrated in FIG. 2, atemperature controller 210 and a furnace 220 in which the carboncontaining precursor (e.g., 1,8-dibromonaphthalene (1,8-DBN)) can beplaced in solid form on support 230. Heating of the furnace undercontrol of the temperature controller can produce the appropriate amountof the carbon containing precursor in the vapor phase. Accordingly,embodiments of the present invention can utilize solid-phase andliquid-phase carbon containing precursors as well as gas-phaseprecursors.

FIG. 3 is a simplified flowchart illustrating a method of growinggraphene nanostripes according to an embodiment of the presentinvention. The method 300 includes providing a substrate (310) andsubjecting the substrate to a reduced pressure environment (312). In anembodiment, the processing chamber was pumped down to 27 mTorr. Duringthe growth of the graphene nanostripes, the total pressure in theprocessing chamber was maintained at 500 mTorr with 2 sccm hydrogenutilized as a carrier gas. The method also includes providing methanegas and a carbon containing precursor (314) and generating a plasma(316). The partial pressure ratio of the methane gas and the carboncontaining precursor (e.g., 1,2-DCB) was controlled, as discussed above,by operation of precision leak valves 137 and 139. The partial pressureof the gases in the processing chamber was monitored by use of RGA 155.Typical methane and 1,2-DCB partial pressures were (10˜900)×10⁻⁹ Torrand (1˜10)×10⁻⁹ Torr, respectively (this is the pressure in the RGA).For remote plasma operation, hydrogen plasma was formed away thesubstrate and then moved to the substrate in order to prevent any plasmatransient damages. Typical plasma power ranges from 4060 W and growthtime ranges from 5˜20 minutes were utilized in some embodiments. Asdiscussed below, the gas flows can be initiated and stabilized beforethe plasma is generated (i.e., 318/320) or the plasma can be turned onprior to the gas flows are initiated (316/318).

The method further includes exposing at least a portion of the substrateto at least the methane gas, the carbon containing precursor, and theplasma (318). The growth of graphene nanostripes coupled to the at leasta portion of the substrate results (322).

Embodiments of the present invention contrast with vertical graphenesheets that are grown after pretreatment of the substrates andadditional substrate heating from 500° C. to 1000° C. since embodimentsof the present invention utilize a single-step, low-power growth processthat requires neither active heating nor pretreatment of the substratesthrough the use of carbon containing precursors (e.g., 1,2-DCB) asseeding molecules for the vertical growth of graphene nanostripes.

FIGS. 4A-4C are simplified schematic diagrams illustrating a seededgrowth process for graphene nanostripes according to an embodiment ofthe present invention. In FIGS. 4A-4C, 1,2-DCB is used as seeds forvertically aligned carpets of graphene nanostripes grown on Cu surfaces,but other carbon containing precursors including C₆ containingprecursors can be utilized, including carbon based, substitutedaromatics such as 1,2-dibromobenzene (1,2-DBB), 1,8-dibromonaphthalene(1,8-DBN), and toluene. Additionally, substrates other than copper foil,including transition metal substrates such as nickel foam, Ni foil,cobalt, or platinum can be utilized.

The hydrogen plasma with a slight trace of CN radicals is used to removethe surface copper oxide and expose a fresh copper surface upon whichthe 1,2-DCB molecules can seed, resulting in the initial formation ofvertical graphene nanostripes. Additionally, methane is introduced intothe hydrogen plasma as another carbon source to enhance the growth rate.In some embodiments, hydrogen is utilized as a carrier gas.

The inventors believe, without limiting embodiments of the presentinvention, that atomic hydrogen and CN radicals are the plasma speciesacting upon copper during the PECVD graphene nanostripe growth process.Atomic hydrogen is produced via the hydrogen plasma and removes nativeatmospheric derived species including Cu₂O, CuO, Cu(OH)₂, and CuCO₃. TheCN radicals are highly reactive with and remove copper prior to andduring graphene growth. Thus, the presence of both atomic hydrogen andCN radicals in the plasma enables the concurrent (e.g., simultaneous)preparation of the copper surface and deposition of high qualitygraphene at reduced temperatures. In addition to CN radicals, othernitrogen oxides, nitrogen oxide radicals, carbon oxides, and/or carbonoxide radicals (e.g., CO, CH, CN, NO, and the like) can be present inthe chamber during growth and provide reactive functionality. Asdiscussed in additional detail in relation to FIG. 11, CN and HCNpartial pressures measured during graphene nanostripe growth andcoincident with plasma generation in the processing chamber indicate theactivity associated with the cyano radicals.

In FIG. 4B, benzene rings are formed as chlorine is removed from 1,2,DCB by the plasma to form HCl and the benzene rings. The addition ofadditional benzene rings results in growth of the graphene nanostripe asillustrated in FIG. 4C.

In contrast with conventional thermal growth techniques, embodiments ofthe present invention utilize carbon containing precursors that havesingle benzene ring structures, thereby enabling integration of not justC₂ radicals, but also C₆H₆ molecules into the matrix of the graphenenanostripe after plasma enhanced decomposition of the single benzenering precursor. Additional description related to both C₆ radicals andC₆H₆ molecules is provided in relation to FIGS. 10 and 12.

Additionally, embodiments of the present invention utilize lowtemperature, CMOS compatible plasma enhanced growth processes thateliminate technological limitations imposed by thermal CVD processes,enabling graphene nanostripe growth that is suitable for integrationwith complementary metal-oxide-semiconductor (CMOS) microelectronicfabrication processes and technology. Since conventional thermal CVDgraphene growth processes operate in temperature ranges exceeding 800°C., these thermal CVD growth processes are incompatible with standardCMOS processes that operate at temperatures less than 450° C. Forexample, the low temperature, e.g., less than 450° C. growth processesdescribed herein are compatible with temperature restrictions to protectmetal interconnects, prevent diffusion of implanted dopant species, andthe like fabricated during a CMOS process. It should be noted that thelow temperature process utilized according to embodiments of the presentinvention enables the use of plastic substrates, for example, plasticcoated with an appropriate metal that can be used as a flexible device.

FIGS. 4D-4J are simplified schematic diagrams illustrating a mechanismfor growth and branching of graphene nanostripes according to anembodiment of the present invention. As illustrated in FIGS. 4D-4J, agrowth mechanism along the zigzag edges of graphene nanostripes isshows. A similar mechanism may take place along the armchair edge, butat a slower rate due to steric hindrance of both edge chlorination(chemical activation) and 1,2-DCB attachment.

Alternatively, 1,2-DCB molecules may selectively attach to zigzag edgeswhile carbon radicals attach to both armchair and zigzag edges as hasbeen proposed in the growth of vertically oriented graphene sheets.Either case is consistent with the large aspect ratios of the graphenenanostripes described herein.

Additionally, the prominent presence of C₆ radicals and C₆H₆ moleculesin the plasma growth process as illustrated in FIG. 10 is likelyimportant for increasing the growth rate and yield of graphenenanostripes because graphene structures can be more effectivelyassembled from these molecules than from C₂ radicals alone. Accordingly,the inventors believe, without limiting embodiments of the presentinvention, that both 1,2-DCB precursor molecules and the resulting C₆,C₆H₆, and chlorine radicals in hydrogen plasma are important formediating rapid vertical growth of graphene nanostripes with largeaspect ratios.

After initial vertical nucleation of a few honeycomb lattices on thecopper substrate as illustrated in FIG. 4A, the graphene edges may bechlorine terminated due to chlorine radicals dissociated from 1,2-DCB.These chlorine terminated edges are chemically activated because ofelectron withdrawal from carbon atoms. Thus, electron-rich aromaticspecies (e.g., 1,2-DCB and its derivatives) can be drawn to the electrondeficient carbon atoms. Given that the zigzag edges of graphene are morelikely to react with chlorine or 1,2-DCB molecules due to sterichindrance at the armchair edges, we first consider the growth mechanismalong the zigzag edges. As depicted in FIG. 4D, a 1,2-DCB molecule mayattach to the graphene zigzag edge via nucleophilic aromaticsubstitution and produce HCl (FIG. 4E) by reaction with either nearbyhydrogen atoms or hydrogen plasma to restore the sp² hybridization, asillustrated in FIG. 4F. The production of HCl is consistent with our RGAdata, and restoring sp² hybridization is energetically favorable.

Conversely, the plasma processes may create radical-terminated grapheneedges that react with radicals derived from 1,2-DCB. Furthermore, the1,2-DCB molecule may react with hydrogen plasma and lose both chlorineatoms to become either benzene or C₆ radicals, which are highly reactivearomatics that could react with graphene edges.

Based on our RGA data discussed herein, all of these growth mechanismsmay contribute the attachment of aromatic rings to graphene nanostripes.The aforementioned steps are repeated to yield the configuration shownin FIG. 4G. Finally, spatial gaps between edges with 1,2-DCB moleculesattached can be filled in with carbon radicals dissociated from eithermethane or 1,2-DCB to complete the graphene lattice illustrated in FIG.4H. When excess 1,2-DCB is present, the graphene edges may becomesaturated with 1,2-DCB molecules, i.e., 1,2-DCB molecules may attach toadjacent graphene edge sites as in FIG. 4I. Saturation of the grapheneedges with 1,2-DCB molecules will necessarily result in strain andbranching due to steric hindrance. The sp³ branching at the strainedgraphene sites may be achieved by the attachment of chlorine radicals(FIG. 4J), which is consistent with our EDS observation that chlorine isprimarily present at the branching sites of nano-flowers grown underexcess 1,2-DCB.

On the other hand, when 1,2-DCB is relatively dilute, the graphenezigzag edges are more likely terminated by hydrogen, which could eitherreact with the Cl atom in 1,2-DCB, release HCl while extending thelength of graphene, or simply react with carbon radicals dissociatedfrom either methane or 1,2-DCB to further the growth of graphene.

FIG. 5 is plot illustrating partial gas pressure as a function of timeduring graphene nanostripe growth according to an embodiment of thepresent invention. The partial gas pressure recorded in FIG. 5 wasmeasured in the RGA, not in the growth chamber. In FIG. 5, the 1,2-DCBpartial pressure (e.g., measured using the RGA) is plotted as a functionof time. When the 1,2-DCB is turned on, as illustrated at ˜30 minutes,an initial, high 1,2-DCB partial pressure surge is observed, with the1,2-DCB partial pressure increasing rapidly for approximately one minuteand then decreasing. After a period of approximately nine minutes, the1,2-DCB partial pressure reaches a stable state. As described herein,the inventors have determined that the turn-on sequence of the carboncontaining precursors impacted the morphology of the graphenenanostripes. In particular, since most embodiments utilize a growth timeof about 10 minutes, the high 1,2-DCB/CH₄ partial pressure ratio afterinitial turn on can saturate the substrate, lead to a high density ofnucleation sites, and therefore, an overall decrease in the lateral sizeof the graphene nanostripes.

In an embodiment, the partial pressure reaching a stable state can bedefined in terms of fitting an exponential decay to the partial pressurecurve illustrated in FIG. 5 and stability is reached once theexponential decay term decreases to a predetermined multiple of thedecay constant, for example, three times the decay constant. As anexample, the partial pressure (y) as a function of time (t) can bedetermined by fitting the curve in FIG. 5:

$\begin{matrix}{y = {{2.91 \times 10^{- 9}} + {5.06 \times 10^{- 9}{e^{\frac{({t - 31})}{2.25}}.}}}} & (1)\end{matrix}$

Accordingly, if stability is defined as a time period equal to threetimes the decay constant of 2.25 minutes, stability is reached in ˜7minutes.

FIG. 6 is an SEM image of a graphene nanostripe structure grown with asmall precursor concentration ratio according to an embodiment of thepresent invention. During the growth of the graphene nanostripesillustrated in FIG. 6, the 1,2-DCB/CH₄ partial pressure ratio was 1.5.The total gas pressure was 500 mTorr and the flow rate of H₂ was 2 sccm.The H₂, CH₄, and 1,2-DCB/CH₄ partial pressure ratio were established instable states (1,2-DCB partial pressure ratio kept constant at ˜3×10⁻⁹Torr, as measured in the RGA) and then the plasma (e.g., 60 W) wasturned on. The resulting graphene nanostripes had typical lengths of afew microns to a few tens of microns and relatively large aspect ratiosas shown in FIG. 6. As an example, the length:width aspect ratios ofgraphene nanostripes grown using embodiments of the present inventioncan range from 10:1 to 130:1. Similar results were achieved for1,2-DCB/CH₄ partial pressure ratios less than 1.5.

FIG. 7 is an SEM image of a graphene nanostripe structure grown with alarge precursor concentration ratio according to an embodiment of thepresent invention. During the growth of the graphene nanostripesillustrated in FIG. 7, the 1,2-DCB/CH₄ partial pressure ratio was 2.4.In this case, the plasma was turned on before the flow of the carboncontaining precursor was initiated. As a result, growth occurred duringthe high partial pressure ratio surge illustrated in FIG. 5 at about 30minutes. As shown in FIG. 7, the high partial pressure ratio growthregime resulted in graphene nanostripes with increased branchingphenomena, giving rise to a highly branched, flower-like nanostructure.

These graphene “nano-flowers” were thinner and shorter than the typicalgraphene nanostripes grown with a smaller 1,2-DCB/CH₄ partial pressureratio. This trend was in part attributed to the high 1,2-DCBconcentration that saturated the substrate and led to a high density ofnucleation sites and therefore an overall decrease in the lateral sizeof the graphene nanostripes. The branching behavior, in addition to theshorter lengths of the graphene nanostructures, may be attributed to thelarge amount of 1,2-DCB that resulted in excess chlorine ions terminatedalong the edges of the graphene nanostripes and activated the formationof the branching behavior. This scenario is consistent with studies ofthe ultraviolet photoelectron spectroscopy (UPS), TEM andenergy-dispersive x-ray spectroscopy (EDS) of graphene nanostripes asconducted by the inventors. Thus, the morphology of the graphenenanostripes was strongly dependent on whether the carbon containingprecursor (e.g., 1,2-DCB) was turned on before or after the plasma wasturned on.

TEM images of the nano-flowers indicate that these structures generallyconsisted of a large number of layers, with numerous branching pointsand reorientations of the layers. A significant chlorine peak in the EDSdata was observed at a large number of branching and reorientationlocations in the nano-flower samples. This presence of a distinctchorine peak in a branching region of the nano-flowers is in starkcontrast to the absence of any chlorine signal in the flat region of thesame samples.

FIG. 8 is a Raman spectra for a graphene nanostripe structure grown witha small precursor concentration ratio according to an embodiment of thepresent invention. The spectra illustrated in FIG. 8 was collected for agraphene nanostripe structure with a 1,2-DCB/CH₄ partial pressure ratioof 1.5. FIG. 9 is a Raman spectra for a graphene nanostripe structuregrown with a large precursor concentration ratio according to anembodiment of the present invention. The spectra illustrated in FIG. 9was collected for a graphene nanostripe structure with a 1,2-DCB/CH₄partial pressure ratio of 2.4. Raman spectra were taken via a RenishawM1000 micro-Raman spectrometer system using a 514.3 nm laser (2.41 eV)as the excitation laser source.

The peak at ˜2,700 cm⁻¹ is known as the 2D-band that represents adouble-resonance process of graphene; the peak at ˜1,590 cm⁻¹ is theG-band associated with the doubly degenerate zone-center E_(2g) mode ofgraphene, and the peak at ˜1,350 cm⁻¹ is the D-band that corresponds tozone-boundary phonons due to defects, edges, and/or folds of graphenesheets. Given that the laser spot of the Raman spectrometer (˜1 μm) islarger than the typical widths 10's to 100's of nanometers) of thegraphene nanostripes, we attribute the intense D-band associated withthe graphene nanostripes to the prevailing presence of edges and/or thepresence of folds as observed in SEM and transmission electronmicroscopy (TEM) images. Further, the 2D-to-G intensity ratio,(I_(2D)/I_(G)), is typically greater than one and that thefull-width-half-maximum (FWHM) of the 2D-band is relatively sharp, whichseems to suggest that the graphene nanostripes are largely monolayer.

As can be determined by examining FIGS. 8 and 9, the 2D to G intensityratios, (I_(2D)/I_(G)), and D to G intensity ratios, (I_(D)/I_(G)), varyfor graphene nanostripes grown at different 1,2-DCB/CH₄ partial pressureratios. The (I_(2D)/I_(G)) ratio decreases with the increase of1,2-DCB/CH₄ partial pressure ratio, suggesting that more layers ofgraphene nanostripes were grown with larger amounts of 1,2-DCB. On theother hand, the (I_(D)/I_(G)) ratio increases with the increase of1,2-DCB/CH₄ partial pressure ratio, which is consistent with more edgesdue to branching. Additionally, the in-plane sp² crystallite size(L_(a)) of the GNSPs may be estimated by using the (I_(D)/I_(G)) ratioand the following empirical formula:

$\begin{matrix}{{{L_{\alpha}({nm})} = {\frac{560}{E_{L}^{4}}( \frac{I_{D}}{I_{G}} )^{- 1}}},} & (2)\end{matrix}$

where E_(L) denotes the excitation energy of the laser source, which is514 nm for the Raman spectrometer utilized to obtain the data in FIGS. 8and 9. The inventors have determined that the crystallite size L_(a) andthe work function Φ of the graphene nanostripes decrease steadily withincreasing 1,2-DCB/CH₄ partial pressure ratio.

FIG. 10 is a plot illustrating partial gas pressures as a function oftime during graphene nanostripe growth with a small precursorconcentration ratio according to an embodiment of the present invention.In the process characterized in FIG. 10, the flow of the carboncontaining precursor (e.g., 1,2-DCB) was initiated before turning on theplasma. As a result, the gas pressures had stabilized as discussed inrelation to FIG. 5, as illustrated at zero minutes in FIG. 10, beforethe plasma was initiated at 0.4 minutes, indicated by the shaded regionof the plot. Total chamber pressure was 0.5 Torr, with the majority ofthe chamber pressure arising from the presence of hydrogen.

FIG. 11 is a plot illustrating additional partial gas pressures as afunction of time during graphene nanostripe growth with a smallprecursor concentration ratio according to an embodiment of the presentinvention.

Referring to FIGS. 10 and 11, the use of the RGA to monitor the gases inthe growth chamber during the PECVD process is illustrated. The spectrumin FIG. 10 reveals that hydrogen chloride (HCl) is a main byproduct ofthe PECVD graphene nanostripe growth process as 1,2-DCB in thisembodiment is decomposed to form benzene rings and Cl, which reacts withfree hydrogen. This indicates that hydrogen radicals can react withchlorine released from 1,2-DCB to form hydrogen chloride and render theresulting vertical GNSPs mostly free of chlorine. Additionally,substantial amounts of C₂ and C₆ radicals together with C₆H₆ moleculesare found during the plasma growth process and are likely playing animportant role in enhancing the aspect ratio of the graphene nanostripebecause graphene structures can be more effectively assembled from thesemolecules. It should be noted that while C₂ are radicals present inthermally assisted CVD growth, the presence of C₆ radicals and C₆H₆molecules are unique to the low-temperature PECVD process describedherein as plasma enhanced formation of C₆ and C₆H₆ occurs as theC₆-containing precursors are decomposed in hydrogen plasma.

In FIG. 10, the benzene pressure in the processing chamber issubstantially zero prior to initiation of the plasma, sharply increaseswhen the plasma is initiated, and stabilizes at a pressure of ˜1×10⁻⁴Torr as the growth process proceeds. The generation or production ofbenzene during the growth process results from the plasma enhancednature of the growth process and distinguishes embodiments of thepresent invention from thermal CVD processes.

As illustrated in FIG. 11 and discussed in relation to FIG. 4A, CN andHCN radicals are produced when the plasma is turned on, thereby cleaningthe substrate surface in preparation for graphene growth. It should benoted that since the HCl partial pressure in the residual gas analyzeris represented by mass 36, the presence of other gases with mass near 36(e.g., argon, CCl₄, H₂S, and propyne (CH₃—C═CH)) can result in anartificially high measurement of background mass 36 partial pressurebefore turning on the hydrogen plasma, particularly because argon gashas been used for flushing the growth chamber before the synthesis ofGNSPs. Accordingly, as shown in FIG. 10, the adjusted increase in HClpartial pressure during growth is indicated.

FIG. 12 is a plot illustrating additional partial gas pressures as afunction of time during graphene nanostripe growth with a largeprecursor concentration ratio according to an embodiment of the presentinvention. In the process characterized in FIG. 12, the flow of thecarbon containing precursor (e.g., 1,2-DCB) was initiated after turningon the plasma. As a result, the gas pressures are generally increasingduring the plasma exposure, indicated by the shaded region of the plot.Total chamber pressure was 0.5 Torr, with the majority of the chamberpressure arising from the presence of hydrogen. In comparison with FIG.10, the HCl pressure at zero minutes in FIG. 12 is approximately ¼ ofthe HCl pressure at zero minutes illustrated in FIG. 10, with the HClpressure continuously increasing and only reaching levels shown in FIG.10 at the end of the growth process in FIG. 12.

In FIG. 12, the benzene pressure in the processing chamber issubstantially zero prior to initiation of the plasma and beginsincreasing when the plasma is initiated. The benzene pressure continuesto increase during the growth process as the 1,2-DCB is decomposed andreaches pressures of ˜1×10⁻⁴ Torr as the growth process proceeds. Afterthe plasma is terminated, the benzene pressure drops rapidly as theplasma enhanced growth process terminates.

In FIG. 12, the gas pressures have reached a steady state, i.e.,stabilized, prior to exposing the substrate to plasma, indicated by theunshaded region between 0 minutes and ˜0.9 minutes. Accordingly, whenthe plasma exposure is initiated, pressure changes for the gases resultsfrom the plasma enhanced growth process, not variations in processinputs associated with stabilization of gas flow rates. As illustratedin FIG. 4B and FIG. 12 when considered together, plasma enhancedbreaking of the 1,2-DCB bonds results in the formation of HCl, whichstarts increasing in concentration in the processing chamber coincidentwith plasma exposure, and in the decomposition of 1,2-DCB as the plasmaenhanced bond breaking occurs. After the plasma is turned off, the1,2-DCB pressure increases and the HCl pressure decreases as the plasmaenhanced growth process is terminated.

FIGS. 13A-13C are plots of ultraviolet photoemission spectroscopy (UPS)data collected under differing graphene nanostripe growth conditionsaccording to an embodiment of the present invention. In FIGS. 13A-13C,the 1,2-DCB/CH₄ partial pressure ratio is 1.5, 1.8 and 2.4,respectively. The UPS measurements were performed via theKratos-Ultra-XPS model, which uses a magnetic immersion lens with aspherical mirror and concentric hemispherical analyzers with adelay-line detector for both imaging and spectroscopy. He I (21.2 eV)were used as excitation sources for UPS measurement in an ultrahighvacuum chamber with a base pressure of 2×10⁻¹⁰ Torr.

UPS experiments were conducted to investigate the work functions ofGNSPs grown under different 1,2-DCB/CH₄ partial pressure ratios and toprovide direct information about possible doping effects on GNSPs. Asshown in FIG. 13A, the work function value (Φ) deduced from thesecondary electron cutoff of the UPS spectrum was found to be 4.45 eVfor GNSPs grown with a 1,2-DCB/CH₄ partial pressure ratio=1.5, which isa value close to that of pristine graphene (˜4.5 eV). The work functionvalue decreased to 4.16 eV for GNSPs grown with a 1,2-DCB/CH₄ partialpressure ratio increased to 2.4, implying significant electron doping.This finding suggests that excess 1,2-DCB not only resulted in theformation of branches and excess chlorine in the GNSPs (see TEM and EDSresults) but also introduced additional electron doping. Thus, asillustrated in FIGS. 13A-13C, as the partial pressure ratio increases,the ultraviolet photoelectron spectroscopy (UPS) data shows increasingelectron doping.

The inventors characterized nanoscale structural properties and chemicalcompositions of the PECVD-grown GNSPs by means of TEM and EDS.Measurements were initially performed on standard GNSPs similar to thoseshown in FIG. 6 that were grown with a 1,2-DCB/CH₄ partial pressureratio ˜1.5.

FIGS. 15A-15C are TEM top view images of GNSPs with successivelyincreasing resolution from large scale (FIG. 15A) to atomic scale (FIG.15C) images. FIG. 15C is an increased resolution image of the regionindicated by the box in FIG. 15B. From these detailed TEM studies, theinventors determined that the typical size of GNSPs transferred to theTEM grid was 500 nm-1.0 μm in width and 5˜10 μm in length, asexemplified in FIG. 15A. The shorter lengths than those of the as grownGNSPs may be attributed to the TEM sample preparation steps thatinvolved sonication of GNSPs in solution that led to shortened samples.

As illustrated in FIG. 15B, the GNSPs were generally flat over largeareas and exhibited ordered nanoscale structures. High resolution imagestaken on these flat areas further revealed graphene atomic latticestructures, as shown in FIG. 15C. The inventors determined that theGNSPs were mostly multilayers and turbostratic.

FIG. 15D is a selected area diffraction (SAD) pattern of GNSPs for theregion shown in FIG. 15C. As shown by the SAD in FIG. 15D, the sampleexhibited two predominant orientations and exceeded six layers inthickness. This finding of multilayer GNSPs seems to differ from Ramanspectroscopic studies of the same GNSPs that revealed both(I_(2D)/I_(G)) ratios >1 and relatively small FWHM in the 2D-band and sowould seem to imply monolayer GNSPs. However, it should be noted thatthe Raman spectra of multilayer graphene sheets with turbostraticstacking (where individual layers separated by a larger than normalinterlayer distance) were also found to exhibit (I_(2D)/I_(G))ratios >1. Therefore, the results demonstrated from the TEM resultsillustrated in FIGS. 15A-C for standard GNSPs can be reconciled with theRaman spectroscopic studies.

FIGS. 15E-15G are TEM top view images of graphene nanoflowers from largescale (FIG. 15E) to atomic scale (FIG. 15G) images. FIG. 15G is anincreased resolution image of the region indicted by the box in FIG.15F. Measurements were initially performed on nano-flower GNSPs similarto those shown in FIG. 7 that were grown with a 1,2-DCB/CH₄ partialpressure ratio ˜2.3. In contrast to the images taken on standard GNSPs,FIGS. 15E and 15F reveal that nano-flowers generally consisted of alarge number of layers, with numerous branching points andreorientations of the layers. In particular, FIG. 15F shows that in thereoriented graphene region, the number of graphene layers within thefield of view is >20, whereas graphene atomic structures can be resolvedin flat regions, as exemplified in FIG. 15G.

FIG. 15H is a SAD pattern of the sample region shown in FIG. 15G. Inthis flat region of the sample (region a in FIG. 15F), a diffractionpattern is exhibited that provides evidence for multiple layers, withvarying orientations for many individual graphene layers that lead tothe disordered circular pattern.

In addition to studies of the structural properties, nanoscale EDSmeasurements were made on flat, unstrained regions of these standardGNSPs, and found a pure carbon composition without any chlorine or othercontaminates. This finding is in contrast to studies of the nano-flowersamples where chlorine appeared in regions with bifurcations, branchingor strain, as explained below.

FIG. 16 is a plot showing Energy-dispersive X-ray spectroscopy (EDS)data for different regions of a GNSP according to an embodiment of thepresent invention. Plot a in FIG. 16 was obtained by characterizingregion a in FIG. 15F, which is a flat region of the sample. Plot b inFIG. 16 was obtained by characterizing region b in FIG. 15F, which is abranching region of the sample. The inset in FIG. 16 is an expansion ofthe dashed area shown in the main panel.

Plot b in FIG. 16 shows a distinct chlorine peak in a branching region,which is in stark contrast to the absence of chlorine in flat areas suchas the flat region labeled by region a in FIG. 15F. On the other hand,in the branching region of the sample (region b in FIG. 15F), asignificant chlorine peak in the EDS data is observed in conjunctionwith a large number of branching and reorientation locations in thenano-flower samples as exemplified in FIG. 16. Thus, this presence of adistinct chorine peak in a branching region of the nano-flowers is instark contrast to the absence of any chlorine signal in the flat regionof the same samples.

In order to achieve high yields of GNSPs growth, we experimented variousparameters for synthesizing typical GNSPs with 1,2-DCB/CH₄ partialpressure ratios <˜1, as summarized in Table 1. We found that the yieldof GNSPs, determined in units of mass per unit area, increased by morethan one order of magnitude when the power was increased from 40 W to 60W. This finding may be attributed to the presence of more energetic gasmolecules and radicals (particularly C₂, C₆ and C₆H₆) in the plasma toinitiate and maintain the growth of GNSPs. Additionally, higher CH₄partial pressure and longer growth time provided more carbon sources andtherefore also help increase the yield of GNSPs. On the other hand,further increase of either the plasma power above 60 W or the CH₄partial pressure could not result in higher yields, which may be theresult of a limited surface area of the Cu substrate in our growthchamber for initiating the vertical growth of GNSPs. Moreover, excessplasma power tends to increase the amount of C₂ radicals at the expenseof reducing the amount of C₆ radicals and C₆H₆ molecules. Given that C₆radicals and C₆H₆ molecules are likely playing an important role inenhancing the growth rate of GNSPs, proper balance between the plasmapower and the amount of C₆ and C₆H₆ is necessary to achieve high yieldsof GNSPs.

TABLE 1 Experimental parameters for the growth process, showing the gaspartial pressures (measured in the RGA) of 1,2-DCB and CH₄, plasmapower, and time for the PECVD growth of GNSPs. 1,2-DCB CH₄ Power Growthtime Yield (10⁻⁹ Torr) (10⁻⁹ Torr) (W) (min) (μg) 1~10 10~40 40 10 <11~10 10~40 60 10 12 ± 6  1~10 900 60 5 250 ± 280 1~10 900 60 10 530 ±130 1~10 900 60 15 800 ± 270 1~10 900 60 20 1300 ± 430 

By optimizing various growth parameters, we found that the best yieldfor 20 minutes of growth time could reach (1.30±0.43) mg/cm², orequivalently, (13.0±4.3) g/m². The high-yield growth of GNSPs resultedin a completely darkened surface of the substrate due to dense coverageof GNSPs on the metallic substrate. FIG. 17A illustrates opticalmicrographs prior to and after growth of GNSPs according to anembodiment of the present invention. In FIG. 17A, the substrate prior togrowth is illustrated by the sample 1710 marked (a) and the substrateafter growth of GNSPs is illustrated by the sample 1712 marked (b). FIG.17B is a plot showing transmission as a function of wavelength for GNSPsaccording to an embodiment of the present invention. The completelydarkened substrate surface of sample 1712 by the coverage of GNSPs isindicative of strong light absorption by GNSPs, which may be attributedto effective light trapping in stacks of GNSPs due to multiplescattering and has been further corroborated by optical transmissionspectroscopic measurements in FIG. 17B that reveal <0.1% of opticaltransmission for wavelengths from 400 nm to 800 nm. Thus, GNSPs may beconsidered as efficient light absorbers for potential applications tophotovoltaic cells when combined with proper plasmonic nanostructures.

FIG. 14 shows plots of optical emission spectroscopy intensity as afunction of wavelength for PECVD-grown graphene nanostripes underdiffering graphene nanostripe growth conditions according to anembodiment of the present invention. In the optical emissionspectroscopy (OES) plots shown in FIG. 14, the 1,2-DCB/CH₄ partialpressure ratios are 0, 1.5, 1.8, and 2.4, respectively. The OES peaksassociated with CN (388 nm), CH (431 nm), H_(β) (486 nm), C₂ (516 nm),and Hα (656 nm) are shown. As illustrated in FIG. 14, the OES datademonstrates decreasing intensities of all hydrogen related peaks(H_(α), H₂, and H_(β)) with increasing 1,2-DCB/CH₄ partial pressureratio, consistent with the reaction of hydrogen with increasing chlorineradicals. On the other hand, the intensity of C₂ radicals, which theinventors believe, without limiting embodiments of the presentinvention, is important for graphene growth, is enhanced upon theintroduction of 1,2-DCB precursor molecules, although no furtherincrease appears with increasing 1,2-DCB/CH₄ partial pressure ratio.

It is also understood that the examples and embodiments described hereinare for illustrative purposes only and that various modifications orchanges in light thereof will be suggested to persons skilled in the artand are to be included within the spirit and purview of this applicationand scope of the appended claims.

What is claimed is:
 1. A method of forming vertical graphene nanostripescomprising one or several monolayers and characterized by a thicknessnormal to the one or several monolayers, a length orthogonal to thethickness, and a width orthogonal to the thickness, the methodcomprising: providing a substrate consisting of copper foil or nickelfoam; subjecting the substrate to a reduced pressure environment in aprocessing chamber; providing methane gas and C₆-containing precursor;flowing the methane gas and the C₆-containing precursor into theprocessing chamber; establishing a partial pressure ratio ofC₆-containing precursor to methane gas in the processing chamber,wherein the partial pressure ratio is between 0 and 3; generating aplasma; thereafter, exposing the at least a portion of the substrate tothe methane gas, the C₆-containing precursor, and the plasma; andgrowing the vertical graphene nanostripes coupled to the at least aportion of the substrate, wherein one or more of the vertical graphenenanostripes are characterized by the thickness measured parallel to thesubstrate, the length extending parallel to the substrate in a firstdirection, and the width extending orthogonal to the substrate in asecond direction, and an aspect ratio of the length to the width rangingfrom 10:1 to 130:1.
 2. The method of claim 1 wherein the partialpressure ratio is between 1 and
 2. 3. The method of claim 1 furthercomprising generating C₆ radicals in the processing chamber concurrentlywith: exposing the at least a portion of the substrate to the methanegas, the C₆-containing precursor, and the plasma; and growing thevertical graphene nanostripes.
 4. The method of claim 1 furthercomprising generating benzene rings in the processing chamberconcurrently with: exposing the at least a portion of the substrate tothe methane gas, the C₆-containing precursor, and the plasma; andgrowing the vertical graphene nanostripes.
 5. The method of claim 4wherein growing the vertical graphene nanostripes coupled to the atleast a portion of the substrate comprises bonding of benzene rings tothe substrate with carbon atoms of the benzene rings aligned with thelength and the width of the vertical graphene nanostripes.
 6. The methodof claim 5 wherein growing the vertical graphene nanostripes coupled tothe at least a portion of the substrate further comprises bonding ofadditional benzene rings to previously bonded benzene rings with carbonatoms of the additional benzene rings aligned with the length and thewidth of the vertical graphene nanostripes.
 7. A method of formingvertical graphene nanostripes comprising one or several monolayers andcharacterized by a thickness normal to the one or several monolayers, alength orthogonal to the thickness, and a width orthogonal to thethickness, the method comprising: providing a substrate; subjecting thesubstrate to a reduced pressure environment in a processing chamber;providing methane gas and C₆-containing precursor; flowing the methanegas and the C₆-containing precursor into the processing chamber;establishing a partial pressure ratio of the C₆-containing precursor tomethane gas in the processing chamber; generating a plasma; exposing atleast a portion of the substrate to the methane gas, the C₆-containingprecursor, and the plasma; and growing the vertical graphene nanostripescoupled to the at least a portion of the substrate, wherein thethickness of the vertical graphene nanostripes extends parallel to thesubstrate.
 8. The method of claim 7 wherein the substrate comprisescopper foil.
 9. The method of claim 7 wherein the partial pressure ratioranges from 0 to
 3. 10. The method of claim 9 wherein the partialpressure ratio is between 1 and
 2. 11. The method of claim 7 furthercomprising generating C₆ radicals in the processing chamber concurrentlywith: exposing the at least a portion of the substrate to the methanegas, the C₆-containing precursor, and the plasma; and growing thevertical graphene nanostripes.
 12. The method of claim 7 furthercomprising generating benzene rings in the processing chamberconcurrently with: exposing the at least a portion of the substrate tothe methane gas, the C₆-containing precursor, and the plasma; andgrowing the vertical graphene nanostripes.
 13. The method of claim 12wherein growing the vertical graphene nanostripes coupled to the atleast a portion of the substrate comprises bonding of benzene rings tothe substrate with carbon atoms of the benzene rings aligned with thelength and the width of the vertical graphene nanostripes.
 14. Themethod of claim 13 wherein growing the vertical graphene nanostripescoupled to the at least a portion of the substrate further comprisesbonding of additional benzene rings to previously bonded benzene ringswith carbon atoms of the additional benzene rings aligned with thelength and the width of the vertical graphene nanostripes.
 15. Themethod of claim 7 further comprising providing hydrogen gas andgenerating HCl in the processing chamber concurrently with: exposing theat least a portion of the substrate to the methane gas, theC₆-containing precursor, and the plasma; and growing the verticalgraphene nanostripes.
 16. The method of claim 7 further comprisinggenerating CN radicals, nitrogen radicals, nitrogen oxide radicals,carbon oxides, or carbon oxide radicals in the processing chamberconcurrently with: providing a gas including nitrogen; exposing the atleast a portion of the substrate to the methane gas, the gas includingnitrogen, the C₆-containing precursor, and the plasma; and growing thevertical graphene nanostripes.
 17. The method of claim 7 wherein the oneor several monolayers consist of one monolayer.
 18. The method of claim7 wherein the C₆-containing precursor comprises 1,2-dichlorobenzene(1,2-DCB).
 19. The method of claim 7 wherein the length extends parallelto the substrate in a direction orthogonal to the thickness, the widthextends orthogonal to the substrate, and an aspect ratio of the lengthto the width ranges from 10:1 to 130:1.
 20. The method of claim 7further comprising generating C₆ and C₂ radicals during exposing the atleast a portion of the substrate to the methane gas, the C₆-containingprecursor, and the plasma.